Patent GB-1496310-A (GB)
Title: Manufacture of organosiloxanes
IPC: C08G77/04
Filed: 1976-05-11
Abstract: 1496310 Alkyl halides produced from organohalosilanes and alkanols WACKER-CHEMIE GmbH 11 May 1976 [15 May 1975] 19363/76 Heading C2C [Also in Division C3] A process for the manufacture of an organosiloxane and an alkyl halide comprises passing an organohalogenosilane having one or two halogen atoms into a reaction bed of inert packing material maintained at a temperature of from 60 to 150 C. causing it there to react with methanol or ethanol to produce an alkyl halide and a mixture comprising water and an organosiloxane, causing the said mixture to issue from the reaction bed and separating it into an aqueous phase and an organosiloxane phase, returning a part of the aqueous phase to the reaction bed such that the amount of the aqueous phase returned is from 1-6 litres per mole of the organohalogenosilane initially passed into the reaction bed, and causing the organosiloxane phase to react with an additional 2-10% wt. of the organohalogenosilane based on the organosiloxane phase, and separating the organosiloxane produced. The organohalogenosilane is preferably one of the formulµ R m H n SiX 4-m-n  and R 2 XSi-R<SP>1</SP>-SiXR 2  where X is Cl, Br or I, R denotes an unsubstituted or substituted monovalent hydrocarbon radical, R<SP>1</SP> denotes an unsubstituted or substituted bivalent hydrocarbon radical, m is 1-3, n is 0 or 1 and m+n is 2 or 3. The preferred organohalosilane is dimethyldichlorosilane. The organohalosilane having 1 or 2 halogen atoms may be used in admixture with up to 10% wt. of one or more other halosilanes, e.g. SiCl 4  or methyltrichlorosilane. The alkanol may be passed into the reaction bed or may be manufactured in situ, e.g. by the hydrolysis of a carboxylic acid ester of 2-4 C atoms, e.g. methyl acetate. Suitable packing materials are of ceramics or carbon, sintered powder of polyolefins and silica Xerogels. The reaction bed may also contain Lewis acids and cation-exchangers in the H form. The reaction is preferably carried out at atmospheric pressure. The organohalosilane and alkanol may be fed to the reaction bed co- or counter-currently. Part of the aqueous phase not returned to the reaction bed may be distilled and the alkanol obtained recycled. The alkyl halide may be removed from the top of the reaction tower, if used. The organosiloxane produced may be subjected to steam distillation and any undesired organosiloxane returned to the reactiod bed. The process is preferably carried out continuously. In a preferred continuous process liquid dimethyldichlorosilane is fed through pipes 1 and 1α to evaporator 2 and the resultant vapour passed via pipe 3 into heat reaction tower 4 filled with packing material. Liquid CH 3 OH flows through pipe 6 from inlet pipe 11 into tower 4. Gaseous unreacted CH 3 OH and CH 3 Cl passes out of tower 4 into condenser 7 and the condensed CH 3 OH runs back into tower 4 via pipe 8, and the CH 3 Cl passes into wash tower 10 where it is washed with CH 3 OH and then passes out of tower 10 to a condenser via pipe 12. Material issuing from the lower end of tower 4 is separated into an upper polydimethylsiloxane layer and lower aqueous layer consisting of water, HCl and CH 3 OH. Part of the lower layer is returned via pipes 14 and 16 to tower 4. The rest is conveyed to distillation device 28 and the gaseous methanol issuing from the top of device 28 is condensed in condenser 30 and part of it returned to methanol supply line 11. The upper organosiloxane layer in vessel 13 is mixed in pipe 17 with additional dimethyldichlorosilane brought via pipe 1b and passes into mixing vessel 18 and thence into distillation device 23 where the low boiling point fractions are separated and returned to tower 4 via pipe 34 after separation from the aqueous phase. The linear dimethylpolysiloxanes which are OH- terminated and which are substantially free from alkoxy groups and may have viscosities ranging from 70-200 cS at 25 C. are drawn off through pipe 33.